Azodyestuffs containing copper in



Patented Aug. 18, 1936 PATENT OFFICE AZODYESTUFFS CONTAINING COPPER IN A COMPLEX FORM Detlef Delfs, Rudolf Knoche, and Ernst Messmer,

Leverkusen-I. G.-Werl and Heinrich Clingestein,

Cologne-on-the-Rhine, Germany,

signors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application August 24, 1933. Serial No. 686,652. In Germany September 15, 1932 8 Claims.

The present invention relates to azodyestuffs containing copper in a complex form, more particularly it relates to dyestuifs which may be represented by the probable general formula:

wherein -X- stands for one of the groups R1 and. R2 stand for aromatic radicals of the benzene series to which the azo-bridges are attached in p-position to X and wherein the bridges -OCuO- are attached to R1 and R2 in o-position to the axe-bridges, and wherein R3 and R4 stand for aromatic radicals, such as a radical of the benzene, naphthalene, carbazole series which may bear further substituents, such as the. sulfonic acid group, the carboxylic acid group, alkyl, alkoxy, halogen and the nitro group.

Our new dyestuffs are obtainable by various methods, for example, by tetrazotizing a p, pdiaminomonoazodyestuil of the general formula:

wherein R1 and R2 stand for aromatic radicals of the benzene series, to which the O-alkyl radicals are attached in o-pcsition to the NH2'radicals, coupling with two molecular proportions of the same or difierent coupling components coupling in o position to a hydroxy group and coppering the trisazodyestufi thus obtained with the splitting up of the alkoxy group. Or otherwise our" new dyestufis are obtainable by diazo-' tizingan amine of the type:

M NK,

groups in an alkaline medium according to methods known per se and finally coppering the trisazodyestufls or disazoazoxydyestufis with the splitting up of the alkoxy groups.

nitromonoazodyestufis to.

Further our dyestuffs are obtainable by diazotizing an amino compound of the following type:

coupling with a coupling component coupling in o-position to a hydroxy group, combining two molecules of the nitromonoazodyestufis' to trisazodyestufi's or disazoazoxydyestuifs by reducing the nitro groups to the azoor azoxy groups in an alkaline medium according to methods known per se and finally coppering the trisazodyestuffs or disazoazoxydyestufis with a splitting off of the chlorine atoms inorthOzposition to the am group and formation of the corresponding copper-containing ortho-hydroxy azodyestufis, said method of coppering being more fully described in German specification 571,859, or finally our dyestufis are obtainable by diazotizing one of the amines of the following types:

coupling with a coupling component coupling in o-position to a hydroxy group transforming the monoazodyestufis into copper-containing ohydroxyazodyestuffs, and combining two mole- 3 5. cules of the copper-containing nitro-monoazodyestuffs to trisazodyestuffs or disazoazoxydyestuffs by reducing the nitro groups to the azoor azoxy groups in an alkaline medium according to methods known per se. i

Our new dyestuffs are in form of their alkali metal salts generally dark powders, soluble in water, dyeing the cellulosic fibre generally violet to blue to grey, especially blue, shades of good fastness'properties. .Those dyestufiscapable of further undergoing coupling may be developed on the fibre by coupling with diazo compounds, while those containing diazotizable amino groups may be developed by diazotizing on the fibre and coupling with coupling components, whereby new shades are obtainable.

The invention is illustrated'by the following examples, without being limited thereto:

Example 1.-'-55.3 parts by weight of the sodium saltpf t e tufi' r m ecu ar P P Q of 4,4 hiamine-5,5',-dimethoxy- 2 g methyl-1,1

azobenzene-2-sulfonio acid and 2 molecular proportions of l-hydroxynaphthalene lfi-disulfonic acid are dissolved in'3000 parts by weight of water and. after adding 30 parts by weight of crystallizedc opper. sulfate and a mixture of 100 parts by weight of aqueous ammonia of 25% strength and 200 parts by weight of water, the solution is heated for 10 hours at 85 (1., While stirring. "The dyestuff having inrthe free state thefollowing formula: V V

is isolated by salting out, filtered and dried. In 7 its free state itis a dark, bronze lustrous powder, whichisrsoluble' in water; with a blue. coloration. The vegetable fibre is dyed blue shades of good fastness to light.

In an analogous manner there can be coppered other .azodyestufis from one molecular proportion 7 .tetrazotized 4,4-diamino-5,5'-dimethoxy- 1,1-azobenzene ora substitution product thereof and two molecular proportions of the same: or

different coupling component coupling in orthoposition with respectrtoja'hydroxy group. Thus,

the dyestuif from one molecular proportion of tetrazotized "4,4'-diamino-5,5 dimethoxy 1,1-

: azobenzene and twomolecular'proportions of 2-' amino"- 5 -hydroxy naphthalene 1,7 g disulfonic acid yields a copper complex compound, dyeing V cellulosicifibres greenish blue shades of good fast ness tolight.

. 1 Example Z p-52.7 parts by weight of the monoa zodyestuff from diazoti'zed '5-nit'ro2-amino-1- 'm'ethoxybenzene and the sodium salt of 1-hydrriXynaphthaIene-Bfi-disulfonic acid are dissolved in 3000 parts by weight of water'and 90 parts by; weight of aqueous caustic sodalye of 38 7 B.'strength. At '75-80 C. there is slowly'introw 'weight'of grape sugar in 100 parts byweight of' water. When-thereduction is complete, the dye- .duced; while stirring, a solution of 12 parts by stuff is isolated by salting out and is dried. 100

V parts by weight of the dyestuif thus obtained are dissolved in 3500 parts by weight of water and,

Hoes 7 after t e addition of'30 partsby, weight ofcrystallized copper sulfate-anda'mixture of 90 parts by weight of. aqueous ammonia. 013.25% strength 'and 200. parts by weight of water, the solution is heated for 8 hours'at80-90" C., while stirring.

The dyestufi having. in its free state the following 7 with a greenish-blue coloration, dyeing the vegetable fibre blue shades of excellent fastness to light. a

Dyestuffs having similar properties are obtained when substituting the l-hydroxynaphthalene-ifi disulfonic acid by equivalent quantities of 8- fchloro -'1 hydroxynaphthalene 3,6 disulfonic acid or of 1-hydroxynaphthalene-3,8- or 4,7- or -4,8-disulfonic acid, or by substituting the 5-ni-.-

'tro-2ramino-l-methoxybenzene by. equivalent quantities of 5-nitro-4 chloro 2-amino-1-meth O S 03H '2 s the reduction. Asageneralrule; however, there a 7 may be stated that temperatures between about; 7

and about 90 C. are suitable for performing the reduction. f

Example 3. 52.7parts by weight of the monoazodyestufi from diazotized 5-nitro2 amino-l methoxybenzene and the sodium salt of 'Z-hy Vdroxynaphthalene-5,7-disulfonic acid are dissolved'in 3000 parts byweight of water and parts by weight of aqueous caustic soda lye of 38 Be. At 65-70 '0. there is slowly introduced, while stirring, a solution of 12 parts by weightofgrapel sugar and 100 parts'by weight of water; 'Whe n the reductionis complete, the dyestuff is salted out, filtered and dried. a r r V v190 parts, by weight of the dyestufl thus obtained are dissolved in 2500. parts by-weight of water and heated to C. 'To the solution'there is added, while stirring, a solution of 33 parts by weight of crystallized copper sulfate and parts'by weight of aqueous ammonia of 25%' strength in 250 parts by weight of water. 'The mixture is stirred for about 12 hours at 80-90 0., and the dyestuff having in its free state the following formula: w

-15 isolated by salting out. It dyes the vegetame fibre blue shades of good fastness to light and boiling. r

Dyestuffs of similar properties are obtained when substituting the 2-hydroxynaphthalene 5fidisulfonic acid by the 2-hydrox'ynaphthalene-3,6- (or -3,7). disulfonic' acid.

Wis isolated by salting out. i It is obtainedafter Example. 4.-'58.3 parts by weight of the mono- 7'5" drying in form of a dark powden'soluble in water azodyestufi obtainable by coupling in an alkaline medium diazotized 5-nitro-2 amino-1-methoxybenzene and 2- (3-carboxypheny1) amino-8- hydroxynaphthalene-6-sulfonic. acid ,(disodium salt) are suspended in 5000 parts by weight of water and 60 parts by weight of aqueous caustic soda lye of 38 B. strength. The mixture is heated to 65-70" C., thereto is slowly introduced a solution of 13 parts by weight of grape sugar in 100 parts by weight of water.- When the reduction is complete, after about 2 hours, the dyestuff is isolated by salting out, filtered and dried. 100 parts by weight of the dyestufi thus obtained are dissolved in 5000 parts by weight of water, and after the addition of a solution of 30 parts by weight of crystallized copper sulfate and 90 parts by weight of aqueous ammonia of 25% strength in 250 parts by weight of water, the solution is heated for about 12 hours at C., while stirring. The dyestuff having in its free state the following formula:

O I I Hum-N=N N=N- soan or COOH 7-sulfonic acid or the 2-amino-5-hydroxynaph-- thalene-L'T-disulfonic acid. The dyestuff prepared with the aid of 2-(4-carboxyphenyl) amino-8-hydroxynaphtha1ene 6 sulfonic acid has in the free state the following formula:

COOH

(wherein -X- stands forith'e groups :N =N- or i A Y the mentioned foregoing examples I The new sols V riots. O

copper containing "azodyestufi having" in its free state the following formula:

isobtained asa dark powder; soluble in water with a dull bluish-violetcoloration, dyeing cotton and regenerated cellulose bluish-black shades.

V By substituting the 1-hydroxycarbazole-3,6-disulfonic acid by equivalent quantities of 1,8- or N N- NE HOaS 2,8-dihydroxycarbazole-3,6-disulfon1c acid, there are obtained dyestufis dyeing the vegetable fibre grey shades.

Example 6.57 parts by weight of the sodium salt of the monoazodyestufi from diazotized 4- nitro-2-chloro-l-aminobenzene and 8-chloro-1- hydroxynaphthalene-3,6-disulfonic acid are dissolved in'5000 parts by weight of water, 60 parts by weight of aqueous caustic soda lye of 38 B. are added, and at 65 C. a solution of 15 parts by weight of grape sugar in 150 parts by weight of water is dropped in in the course of 3 hours. The dyestufif formed is isolated by salting out and dried. It is. dissolved in 3000 parts by weight of water of -95 C., and'thereto is added a mixture of 30 parts by weight of crystallized copper sulfate in 200 parts by weight of water, 30 parts by weight of glycerine and parts, by weight of aqueous caustic soda lye of 38? B.

COOH

strength. After 8 hours stirring at 90-95 C., the dyestufi having in its free state the following formula:

is isolated by salting cutie 'lAfter' drying and .fll-

tering it is obtained as a dark powder; soluble .in water with a blue coloration and dyeing the vegetable fibrejgreenish-blue shades.

I Example 7.59 parts'by Weight of the 'sodium salt of the copper containing monoazo'dyestufi from diazotized 5-nitro-2-aminOr1 -hydroxyben-' zene and 1,8-dihydroxynaphthalene -3,6 disule ionic acid are dissolved in 3000 parts by weight" of water, and thereto are added'100 parts by weight of aqueous caustic soda lye of 38 B. strength. To the solution, there isintroduced in the course of onehour a solution of 20 parts by weight of grape sugar and 200 parts by weight of water. 'When the coloration of the solution does no longer turn to blue,-'it; is acidified with acetic acid, and the dyestufi having in the free state the following formula: I I

o Cu 1 V is isolated by salting out. It dyes cotton and regenerated cellulose greenish-blue shades.

By substituting the 1,8-dihydroxynaphthalene- 3,6-disulionic' acid by equivalent quantities of other coupling components coupling in ortho positionto the hydroxy group, such as l-amirio'fS-hydroxynaphthalene and the N-substitution products thereof, '2-amino-5 -hydrqx aphthalene- '1,7-disulfonic acids, 3'-arnino'-1-hydroxybenzene- 4-sulfonic acid, and working otherwise accord;

similar properties.

ingto the directions given in: paragraph 1 or this example, there are obtained dyestufis, having Those dyestuifs containing diazotizjable amino groups can bediazotized on the fibre and developed with coupling' components to new shades. The above described dyestufi containing as coupling component 1-amino-8-hydroxynaphthalene-3,6-dis u1fonic acid yields, when diazotiz'ed on the'fibre and coupled with LB-diaminobenzene or 2-hydroxynaphthalene, grey or bluish-black Rfand R2 stand for aromatic radicals of the V V 'OV Cu O shades respectively.

W im I a a z 1. Copper-containing azodyestuifs of the gen- V 0 CuO soar Hols wherein -X-- stands for one of the groups benzene series to which'the azo-bridges are attached in p-position to X and wherein the bridges -O-'Cu-'-O-'- are attached to }R1 and R2 in j o-position to the'azo-bridgesgwherein R3 and R4 stand for aromatic radicals being in form of their alkali'metalsalts generally dark powders,

nols

' being in form of its alkali metal salt a dark pow soluble in water, dyeing the cellulosic-fibre gen erally violet to blue to grey shades. r

'a' copper-eontalning azodyestufist of the general formula:

wherein '---X-' for one of the groups 7 R1 andR: stand for'ammatic radicalsiof the benzene-series to which the azo-bridges are at- SO 3H eral formulai 1 Boss wherein X stands for one of the groups N=N- V --N{7--\N V and wherein 3. Copper-containing'azodyestufis of the genfoo soinqgnms stand for radicals of m-hydroxynaphthalene-sulfonic acids; being in form of their alkali metal I salts generally dark powders, soluble in water, dyeing the cellulosic fibre generally violet to'blue. to grey shades.

4. Th'e dyestufl having in following formula:

(wherein for direct the groups and r Y r the free state the der, soluble in water and dyeing the vegetable fibre blue shades of excellent fastness to light.

5. Copper-containing azodyestufis of the general formula:

Ou-O

'HOIS wherein X stands for one of the groups N=N and N N and wherein SOaH HOaS stand for radicals of aminonaphtholsulfonic acids, being in form of their alkali metal salts generally dark powders, soluble in water, dyeing the oellulosic fibre generally violet to blue to grey shades.

6. The dyestufl? having in the free state the following formula:

wherein X stands for one of the groups N=N- and ....N N and wherein SOSH H0 8 stand for radicals of hydroxycarbazole sulfonic acids, being in form of their alkali metal salts generally dark powders, soluble in water and dyeing the cellulosic fibre generally violet to blue to grey shades.

8; The dyestufi having in the free state the following formula:

COOH

(wherein X stands for one of the groups N=N- and being in form of its alkali metal salt a dark powder, soluble in water with a dull bluish-violet coloration and dyeing cotton and regenerated cellulose bluish-black shades.

DETLEF DELFS.

RUDOLF KNOCHE. ERNST MESSMER. HEINRICH CLINGESTEIN. 

